Actinic-light-curable composition, molded polycarbonate resin object with a cured film, and manufacturing method therefor

ABSTRACT

Disclosed is an active energy ray-curing composition containing an active energy ray-curing prepolymer (A) obtainable by a reaction of an acrylic-based prepolymer having a hydroxyl group and an acrylic monomer (a4) having an isocyanate group, an active energy ray-curing compound (B) having a benzotriazole group, another active energy ray-curing compound (C) differing from the (A) component and the (B) component, and inorganic oxide particles (D). The acrylic-based prepolymer having the hydroxyl group is a copolymer that includes an acrylic monomer (a1) having a piperidinyl group, an acrylic monomer (a2) having a hydroxyl group, etc., as monomer units.

TECHNICAL FIELD

The present invention relates to an active energy ray-curingcomposition, polycarbonate resin molded body with cured film, and amanufacturing method therefor.

BACKGROUND ART

Recently, use of a transparent resin plate in place of a glass plate asa window member in contact with the outdoors in a building, etc., isbeing proposed. In particular, an aromatic-polycarbonate-basedtransparent resin plate is excellent in fracture resistance,transparency, lightness, workability, etc., and is thus a promisingmaterial for a window member.

A window member is required to have weather resistance. Also, variousforms of friction and other external forces are applied to a surface ofa window member. A window member is thus required to exhibit highanti-wear performance. In comparison to a glass plate, a transparentresin plate is low in surface hardness and thus readily losestransparency by becoming flawed or worn. There was thus a limit to usinga transparent resin plate as a window member.

Thus, normally a hard coat layer having weather resistance and wearresistance is laminated on a surface of a transparent resin plateproposed for use as a window member (Patent Literature 1 to 4). Acoating agent for forming a hard coat layer of excellent weatherresistance has also been proposed (Patent Literature 5 and 6).

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Patent Application Laid-Open No.    H11-78515-   Patent Literature 2: Japanese Patent Application Laid-Open No.    2003-311908-   Patent Literature 3: Japanese Patent Application Laid-Open No.    2004-27110-   Patent Literature 4: Japanese Patent Application Laid-Open No.    2007-186573-   Patent Literature 5: Japanese Patent Application Laid-Open No.    2000-159828-   Patent Literature 6: Japanese Patent Application Laid-Open No.    2007-238823

SUMMARY OF INVENTION Technical Problem

However, requirement levels related to weather resistance and wearresistance are becoming high and there is an issue that a conventionalcoating composition is not necessarily adequate in weather resistanceand wear resistance.

Thus, an object of the present invention is to provide an active energyray-curing composition capable of forming a cured film of adequatelyexcellent weather resistance and wear resistance. Another object of thepresent invention is to provide a polycarbonate resin molded body withcured film that includes a cured film having adequately excellentweather resistance and wear resistance and a manufacturing methodtherefor.

Solution to Problem

An active energy ray-curing composition according to the presentinvention contains an active energy ray-curing prepolymer (A) obtainableby a reaction of an acrylic-based prepolymer having a hydroxyl group andan acrylic monomer (a4) having an isocyanate group and a (meth)acryloylgroup, an active energy ray-curing compound (B) having a benzotriazolegroup and a (meth)acryloyl group, another active energy ray-curingcompound (C) having a (meth)acryloyl group and differing from the (A)component and the (B) component, and inorganic oxide particles (D). Theacrylic-based prepolymer having the hydroxyl group is a copolymer thatincludes an acrylic monomer (a1) having a piperidinyl group and a(meth)acryloyl group, an acrylic monomer (a2) having a hydroxyl groupand a (meth)acryloyl group, and another monomer (a3) as monomer units.

By the active energy ray-curing composition according to the presentinvention, a cured film of adequately excellent weather resistance andwear resistance can be formed.

Preferably, the active energy ray-curing prepolymer (A) has a numberaverage molecular weight of 3000 to 100000. Preferably, the activeenergy ray-curing prepolymer (A) has a (meth)acryloyl group equivalentof 250 to 1600.

Preferably, the acrylic monomer (a3) includes a compound having afunctional group that contains a fluorine atom. The functional group ispreferably a perfluoroalkyl group.

The active energy ray-curing compound (C) preferably includes a compound(C1) having a (meth)acryloyl group and a group expressed by —(CH₂)₅—.The compound (C1) is preferably a compound expressed by the followinggeneral formula (1).

In formula (1), R¹ indicates a hydrogen atom or a methyl group, aplurality of R¹ in the same molecule may be the same or different, andn, m, l, o, p, and q indicate integers satisfying n+m+l+o+p+q=1 to 12.Preferably, n, m, l, o, p, and q are integers satisfying n+m+l+o+p+q=6to 12.

The active energy ray-curing compound (C) preferably further includes acompound (C2) having a (meth)acryloyl group and no group expressed by—(CH₂)₅—. The compound (C2) is preferably a urethane compound having anaverage of 2 to 15 (meth)acryloyl groups and a urethane group. Thecompound (C2) preferably has a number average molecular weight of 500 to10000.

The active energy ray-curing compound (C) preferably further includes asilicone oil (C3) having a (meth)acryloyl group.

The inorganic oxide particles (D) are preferably SiO₂ particles.

Preferably on the basis of the total amount of the (A) component, the(B) component, and the (C) component, a proportion of the (A) componentis 1 to 50% by mass, a proportion of the (B) component is 1 to 20% bymass, and a proportion of the (C) component is 30 to 95% by mass.

Preferably on the basis of the total amount of the (A) component, the(B) component, and the (C) component, the proportion of the (A)component is 1 to 50% by mass, the proportion of the (B) component is 1to 20% by mass, a proportion of the (C1) component is 5 to 60% by mass,a proportion of the (C2) component is 20 to 80% by mass, and aproportion of the (C3) component is 0.01 to 2% by mass.

Preferably with respect to 100 parts by weight of the total amount ofthe (A) component, the (B) component, and the (C) component, an amountof inorganic oxide particles (D) is 0.1 to 20 parts by weight.

In another aspect, the present invention relates to a polycarbonateresin molded body with cured film. The polycarbonate resin molded bodywith cured film includes a polycarbonate resin molded body and a curedfilm disposed on a surface of the polycarbonate resin molded body andformed by curing of the active energy ray-curing composition accordingto the present invention.

The polycarbonate resin molded body with cured film according to thepresent invention has adequately excellent weather resistance and wearresistance.

In a further other aspect, the present invention relates to a method formanufacturing the polycarbonate resin molded body with cured film. Themanufacturing method according to the present invention includes a stepof forming a film of the active energy ray-curing composition on asurface of a polycarbonate resin molded body and a step of curing theformed film by irradiation of active energy rays to form a cured film.

By the manufacturing method according to the present invention, apolycarbonate resin molded body having adequately excellent weatherresistance and wear resistance can be obtained.

Advantageous Effects of Invention

By the present invention, a cured film having adequately excellentweather resistance and wear resistance can be obtained. The cured filmis also superior in adhesion to a polycarbonate resin molded body, andhigh adhesion can be maintained after a weather resistance test.

Furthermore, according to the present invention, a polycarbonate resinmolded body having adequately excellent weather resistance and wearresistance is provided.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a sectional view of an embodiment of a polycarbonate resinmolded body.

DESCRIPTION OF EMBODIMENTS

A preferred embodiment according to the present invention shall now bedescribed in detail. However, the present invention is not limited tothe following embodiment. In the present specification, “(meth)acryloylgroup” refers to an acryloyl group or a methacryloyl group, and“(meth)acryloyloxy” refers to an acryloyloxy or methacryloyloxy.

An active energy ray-curing composition according to the presentembodiment contains an active energy ray-curing prepolymer (A), anactive energy ray-curing compound (B) having a benzotriazole group,another active energy ray-curing compound (C) differing from the (A)component and the (B) component, and inorganic oxide particles (D). Therespective components shall be described in detail below.

The prepolymer (A) can be obtained by a reaction of an acrylic-basedprepolymer having a hydroxyl group and an acrylic monomer (a4) having anisocyanate group and a (meth)acryloyl group. The prepolymer (A) isformed by reaction of the hydroxyl group of the acrylic-based polymerwith the isocyanate group of the acrylic monomer (a4).

The acrylic-based prepolymer that is used to obtain the prepolymer (A)is a copolymer that includes an acrylic monomer (a1) having apiperidinyl group and a (meth)acryloyl group and an acrylic monomer (a2)having a hydroxyl group and a (meth)acryloyl group as monomer units.

The prepolymer (A) has a piperidinyl group derived from the acrylicmonomer (a1) and a (meth)acryloyl group derived from the acrylic monomer(a4). By action of the piperidinyl group introduced in the prepolymer(A), the cured film formed is specifically imparted with excellentweather resistance. When the cured film is exposed to ultraviolet rays,chemical bonds of polymer chains making up the cured film are broken andradicals are thereby produced. The produced radicals promote breakage ofthe chemical bonds in the cured film. The piperidinyl group introducedin the prepolymer (A) is considered to react with the radicals tothereby deactivate the radicals and suppress progress of breakage ofchemical bonds in the cured film.

The acrylic monomer (a1) is, for example, at least one kind of compoundselected from among 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidineand 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine.

The hydroxyl group that functions as a point of reaction with theacrylic monomer (a4) is introduced into the acrylic-based prepolymer bythe acrylic monomer (a2). The acrylic monomer (a2) is, for example, atleast one kind of compound selected from the group consisting ofmonofunctional (meth)acrylates, such as hydroxyethyl (meth)acrylate,hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate(hydroxy group bifunctional), 2-hydroxy-3-phenoxypropyl (meth)acrylate,N-methylol (meth)acrylamide, hydroxystyrene, hydroquinonemono(meth)acrylate, hydroxyalkyl vinyl ether, and compounds with whichany one of the above compounds are ethylene oxide modified (EOmodified), propylene oxide modified (PO modified), or caprolactonemodified (CL modified), and polyfunctional (meth)acrylates, such as3-(meth)acryloyloxy-2-hydroxypropyl (meth)acrylate, pentaerythritoltri(meth)acrylate, dipentaerythritol penta(meth)acrylate, isocyanuricacid EO modified di(meth)acrylate, etc.

The acrylic-based prepolymer used for obtaining the prepolymer (A) mayfurther include, as a monomer unit, another monomer (a3) differing fromthe acrylic monomer (a1) and the acrylic monomer (a2) and having aradical polymerizable functional group, such as a (meth)acryloyl group.The monomer (a3) is, for example, at least one kind of compound selectedfrom the group consisting of methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate,cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl(meth)acrylate, dicyclopentanyl (meth)acrylate, 2-methoxyethyl(meth)acrylate, polyethylene glycol alkyl ether (meth)acrylate,polypropylene glycol alkyl ether (meth)acrylate, tetrahydrofurfuryl(meth)acrylate, phenoxyethyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, styrene, andmethylstyrene.

The monomer (a3) preferably includes a compound having a functionalgroup that contains a fluorine atom. The weather resistance of the curedfilm can thereby be further improved. As main reasons thereof, thefollowing two are considered.

(1) By incorporation of a C—F bond, which is a stronger bond, in otherwords, has a higher bond energy than a C—H bond, the chemical bonds inthe cured film are made less likely to be broken.

(2) During curing of the film of the composition, the functional groupcontaining the fluorine atom that is introduced in the prepolymer (A)tends to gather and be distributed at a film surface and vicinitythereof, and the piperidinyl group that the prepolymer (A) has thus alsotends to be present concentratedly at the film surface and vicinitythereof. Consequently, degradation of the cured film interior isprevented more effectively.

The fluorine-atom-containing functional group may, for example, be afluorine-substituted alkyl group, aryl group, or aralkyl group. The2,2,2-trifluoroethyl group, the 2,2,3,3,3-pentafluoropropyl group, the3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl group, and thepentafluorophenyl group can be cited as specific examples of thefunctional group.

The compound having the fluorine-atom-containing functional group thatis used as the monomer (a3) is, for example, at least one kind ofcompound selected from the group consisting of 2,2,2-trifluoroethyl(meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate,2-(perfluorobutyl)ethyl (meth)acrylate,3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate,2-(perfluorohexyl)ethyl (meth)acrylate,3-(perfluorohexyl)-2-hydroxypropyl (meth)acrylate,2-(perfluorooctyl)ethyl (meth)acrylate,3-(perfluorooctyl)-2-hydroxypropyl (meth)acrylate,2-(perfluorodecyl)ethyl (meth)acrylate, 2-(perfluoro-3-methylbutyl)ethyl(meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl(meth)acrylate, 2-(perfluoro-5-methylhexyl)ethyl (meth)acrylate,3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (meth)acrylate,2-(perfluoro-7-methyloctyl)ethyl (meth)acrylate,3-(perfluoro-7-methyloctyl)-2-hydroxypropyl (meth)acrylate,1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl(meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate,1H,1H,9H-hexadecafluorononyl (meth)acrylate,1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, and1H,1H,3H-hexafluorobutyl (meth)acrylate. A compound having both afluorine-atom-containing functional group and the hydroxyl group isclassified not as the acrylic monomer (a2) but as the monomer (a3).

The acrylic-based prepolymer having the hydroxyl group can be obtainedfor example by a method of radically copolymerizing the acrylic monomer(a1), the acrylic monomer (a2), and the monomer (a3).

In the copolymerization process, it is preferable that, on the basis ofa total amount of the monomers (a1), (a2), and (a3), a proportion of theacrylic monomer (a1) is 10 to 80% by mass, a proportion of the acrylicmonomer (a2) is 10 to 80% by mass, and a proportion of the monomer (a3)is 0.1 to 20% by mass, and more preferable that the proportion of theacrylic monomer (a1) is 20 to 70% by mass, the proportion of the acrylicmonomer (a2) is 20 to 70% by mass, and the proportion of the monomer(a3) is 1 to 15% by mass.

When a copolymerization ratio of the acrylic monomer (a1) exceeds 80% bymass, the proportion of the acrylic monomer (a2) having the hydroxylgroup is relatively low. Consequently, the amount of the hydroxyl groupthat is to react with the acrylic-based monomer (a4) having theisocyanate group for obtaining the prepolymer (A) is low, and a(meth)acryloyl group equivalent of the prepolymer (A) is large. When the(meth)acryloyl group equivalent of the prepolymer (A) is large, theeffect of wear resistance improvement of the cured film tends to besmall. On the other hand, when the copolymerization ratio of the acrylicmonomer (a1) is less than 10% by mass, the amount of the piperidinylgroup in the prepolymer (A) decreases and the amount of prepolymer (A)required for expressing excellent weather resistance tends to be high.

When a copolymerization ratio of the acrylic monomer (a2) exceeds 80% bymass, the copolymerization ratio of the acrylic monomer (a1) having thepiperidinyl group is relatively low and the effect of weather resistanceimprovement tends to be small. On the other hand, when thecopolymerization ratio of the acrylic monomer (a2) is less than 10% bymass, the (meth)acryloyl group equivalent of the prepolymer (A) is highand the effect of wear resistance improvement of the cured film tends tobe low.

The radical copolymerization is performed in a reaction solutioncontaining the respective monomers and a polymerization initiator. Thepolymerization initiator is selected as suited in accordance withsolubility with respect to the monomers, polymerization temperature,targeted molecular weight, etc. As examples of the polymerizationinitiator, azo-based initiators, such as 2,2′-azobis(isobutyronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyronitrile),1,1′-azobis(cyclohexane-1-carbonitrile),2,2′-azobis[N-(2-propenyl)-2-methylpropionamide],1-[(1-cyano-1-methylethyl)azo]formamide,2,2′-azobis[N-butyl-2-methylpropionamide],2,2′-azobis[N-cyclohexyl-2-methylpropionamide], etc., macroazoinitiators having a polydimethylsiloxane or polyethylene glycol chain,and peroxides, such as diisobutyl peroxide, di-t-butyl peroxide, benzoylperoxide, t-butyl 2-ethylhexanoate,1,1-di-t-butylperoxy-2-methylcyclohexane, etc., can be cited.

An amount of the polymerization initiator with respect to 100 parts byweight of the total amount of the acrylic monomer (a1), the acrylicmonomer (a2), and the monomer (a3) is preferably 0.1 to 10 parts byweight. When the amount of the polymerization initiator is less than 0.1parts by weight, the prepolymer (A) increases in molecular weight and acomposition containing it increases in viscosity. In this case, thecomposition can be decreased in coating aptitude when used as a coating.On the other hand, when the amount of the polymerization initiator isgreater than 10 parts by weight, the acrylic-based prepolymer obtaineddecreases in molecular weight and a proportion of components having nohydroxyl group in the copolymerization reaction product increases.Consequently, components having no (meth)acryloyl group are readilymixed in the reaction product of the prepolymer (A) and the acrylicmonomer (a4). In this case, the composition is lowered in curingproperty and hardness, etc., of the cured film tend to decrease.

The radical copolymerization may be performed in a non-solvent state orin a solvent. As examples of solvents that can be used, toluene, xylene,acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,isophorone, methyl acetate, ethyl acetate, propyl acetate, isopropylacetate, butyl acetate, isobutyl acetate, cyclohexyl acetate,tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate,dietheylene glycol monomethyl ether acetate, methanol, ethanol,1-propanol, 2-propanol, butanol, and diacetone alcohol can be cited.

Although the temperature during the radical copolymerization may berestricted according to the combination of the solvent boiling point andthe initiator in some cases, it is normally 40 to 150° C. and preferably60 to 100° C.

The acrylic-based prepolymer used for obtaining the prepolymer (A) has ahydroxyl value of preferably 30 to 300 (mgKOH/g) and more preferably 70to 270 (mgKOH/g). When the hydroxyl value is small, the amount of the(meth)acryloyl group introduced into the prepolymer (A) is low. That is,the (meth)acryloyl group equivalent of the prepolymer (A) is high. Inthis case, the wear resistance improvement effect of the cured film thatis formed tends to be low. On the other hand, when the hydroxyl value ofthe acrylic-based prepolymer is large, the copolymerization ratio of theacrylic monomer (a1) having the piperidinyl group is low and the weatherresistance improvement effect tends to be low.

The acrylic monomer (a4) that is reacted with the acrylic-basedprepolymer having the hydroxyl group for obtaining the prepolymer (A)is, for example, at least one kind of compound selected from the groupconsisting of monofunctional (meth)acrylates, such as2-(meth)acryloyloxyethyl isocyanate,2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, etc., andpolyfunctional (meth)acrylates, such as1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.

Conditions of the reaction of the acrylic-based prepolymer and theacrylic monomer (a4) are adjusted as suited according to the combinationof the compounds. In order to prevent reaction of the double bondsbelonging to the respective compounds, the reaction temperature ispreferably 20 to 110° C. and more preferably 50 to 100° C.

A polymerization inhibitor may be added during the reaction to preventreaction of the double bonds. As examples of the polymerizationinhibitor, phenol or naphthol derivatives, such as hydroquinone (HQ),hydroquinone monomethyl ether (MEHQ), 2,6-di-t-butyl-4-methylphenol(BHT), t-butylcatechol (TBC), and 4-methoxy-1-naphthol, etc.,phenothiazine derivatives, and nitrosamine salts can be cited. The samepolymerization inhibition effect can also be obtained by blowing inoxygen or air into the reaction system. In a case where thepolymerization inhibitor causes coloration or other problems, it ispreferable to suppress the amount of the polymerization inhibitor to alow amount and perform the reaction while blowing in oxygen or air.

The prepolymer (A) has a number average molecular weight of preferably3000 to 100000 and more preferably 5000 to 50000. A large amount ofcomponents having no (meth)acryloyl group tends to become mixed in aprepolymer (A) of low number average molecular weight. In this case, theactive energy ray-curing composition is lowered in curing property andthe cured film tends to be lowered in hardness, etc. On the other hand,when the number average molecular weight of the prepolymer (A) isexcessively high, the composition becomes too high in viscosity and thecomposition may decrease in coating aptitude when used as a coating. Inmany cases, the molecular weight of the acrylic monomer (a4) hardlyinfluences the number average molecular weight of the prepolymer (A) andit is thus preferable that the acrylic-based prepolymer having thehydroxyl group, which may be said to be a precursor of the prepolymer(A), has a number average molecular weight of 3000 to 100000 as well. Inthe present specification, the number average molecular weight is astandard polystyrene equivalent value determined by GPC measurement.

The prepolymer (A) preferably has a functional group equivalent of thepiperidinyl group (piperidinyl group equivalent) of 200 to 7000 and morepreferably 300 to 4000. Also, the prepolymer (A) preferably has afunctional group equivalent of the (meth)acryloyl group ((meth)acryloylgroup equivalent) of 250 to 1600 and more preferably 300 to 1000. Here,the “functional group equivalent” refers to a mass (g) of the prepolymer(A) per one mole of each functional group.

The active energy ray-curing compound (B) has a benzotriazole group anda (meth)acryloyl group. The benzotriazole group serves a function ofconverting energy of ultraviolet rays to heat energy and therebysuppressing breakage of chemical bonds in the cured film. Thebenzotriazole group is a monovalent group expressed, for example, by thefollowing chemical formula.

The compound (B) is, for example, at least one kind of compound selectedfrom the group consisting of2-(2′-hydroxy-5′-(methacryloyloxyethyl)phenyl)-2H-benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methacryloxyethylphenyl)-2H-benzotriazol e,2-(2′-(meth)acryloyloxy-5′-methylphenyl)benzotriazole,2-(2′-(meth)acryloyloxy-5′-t-octylphenyl)benzotriazole, and2-(2′-(meth)acryloyloxy-3′,5′-di-t-butylphenyl)benzotriazole.

As the active energy ray-curing compound (C), various compounds having a(meth)acryloyl group is used. Preferably, an active energy ray-curingcompound (C1) having a group expressed by —(CH₂)₅— and a (meth)acryloylgroup is used. The group expressed by —(CH₂)₅— is preferably introducedas a bivalent group derived from a caprolactone and expressed by thefollowing chemical formula.

The compound (C1) is preferably a compound expressed by the generalformula (1) cited above. In the formula (1), R¹ indicates a hydrogenatom or a methyl group, and a plurality of R¹ in the same molecule maybe the same or different. n, m, l, o, p, and q indicate integerssatisfying n+m+l+o+p+q=1 to 12. If n+m+l+o+p+q is less than 1, thecoating film tends to peel off readily in a long-term weather resistancetest. From the same standpoint, n, m, l, o, p, and q are preferably suchthat n+m+l+o+p+q is no less than 6. On the other hand when n+m+l+o+p+qexceeds 12, the (meth)acryloyl group equivalent in the compound (C1)increases, the wear resistance of the cured film formed decreases, andthe hardness of the cured film tends to be difficult to maintain. Thecompound expressed by the general formula (1) may be obtained, forexample, by a method of further adding (meth)acrylic acid to an adductof dipentaerythritol and ε-caprolactone.

The curing composition according to the present embodiment may furthercontain, as the compound (C), an active energy ray-curing compound (C2)having no group expressed by —(CH₂)₅—.

As the compound (C2), an oligomer having a number average molecularweight of 500 to 10000 is preferable. The compound (C2) is, for example,preferably at least one kind of oligomer selected from among polyester(meth)acrylates, polyurethane (meth)acrylates, epoxy (meth)acrylates,and (meth)acrylated maleic acid modified polybutadienes. Among these,polyurethane (meth)acrylates are particularly preferable.

A number of (meth)acryloyl groups per molecule of the oligomer ispreferably 2 to 15 and more preferably 4 to 12 on the average. If thenumber of (meth)acryloyl groups is less than 2, the hardness of thecured film decreases and the scratch resistance tends to decrease. Ifthe number of (meth)acryloyl groups is greater than 15, strain in thecured film increases due to increase of curing shrinkage. When thestrain increases, cracking and peeling of the cured film occur readilyduring a weather resistance test. Appearance is damaged greatly whencracking and peeling occur.

The curing composition according to the present embodiment may furthercontain, as the compound (C), a silicone oil (C3) having a(meth)acryloyl group. The silicone oil (C3) contributes to furtherimprovement of the wear resistance of the cured film. As examples ofcommercially available silicone oils (C3), X-22-164, X-22-164AS,X-22-164A, X-22-164B, X-22-164C, X-22-164E, X-22-174DX, X-22-2426,X-22-2475, and X-22-2458 (all made by Shin-Etsu Chemical Co., Ltd.) canbe cited.

In the curing composition according to the present embodiment, it ispreferable that, on the basis of a total amount of the active energyray-curing compounds (A), (B), and (C), a proportion of the (A)component is 1 to 50% by mass, a proportion of the (B) component is 1 to20% by mass, and a proportion of the (C) component is 30 to 95% by mass,and it is more preferable that (A) component:(B) component:(C)component=2 to 45:2 to 15:40 to 90 (% by mass).

In a case where the (C) component includes compounds (C1), (C2), and(C3), it is preferable in the curing composition that, on the basis ofthe total amount of the active energy ray-curing compounds (A), (B), and(C), the proportion of the (A) component is 1 to 50% by mass, theproportion of the (B) component is 1 to 20% by mass, a proportion of the(C1) component is 5 to 60% by mass, a proportion of the (C2) componentis 20 to 80% by mass, and a proportion of the (C3) component is 0.01 to2% by mass, and it is more preferable that (A) component:(B)component:(C1) component:(C2) component:(C3) component=2 to 45:2 to15:10 to 50:30 to 70:0.05 to 1 (% by mass).

From the standpoint of realizing high hardness and improved wearresistance in the cured film, it is important for the curing compositionaccording to the present embodiment to further contain the inorganicoxide particles (D). An amount of the inorganic oxide particles (D),with respect to 100 parts by weight of the total amount of the activeenergy ray-curing compounds (A), (B), and (C), is preferably 0.1 to 20parts by weight and more preferably 0.5 to 15 parts by weight.

As the inorganic oxide particles (D), SiO₂ particles are preferable andcolloidal silica is more preferable. Specifically, a colloidal solution,such as MEK-ST, IPA-ST, and PGM-ST (all organosilica sols made by NissanChemical Industries, Ltd.), in which colloidal silica with a particlediameter of approximately 10 to 100 nm is dispersed in an organicsolvent, such as alcohol, ketone, ester, etc., can be cited.

In a case where ultraviolet rays or visible light is used for curing ofthe curing composition, the active energy ray-curing compositionaccording to the present embodiment further contains aphotopolymerization initiator (photoradical generator).

An amount of the photopolymerization initiator, with respect to 100parts by weight of the total amount of the active energy ray-curingcompounds (A), (B), and (C), is preferably 0.1 to 20 parts by weight andmore preferably 1 to 10 parts by weight.

The photopolymerization initiator (photoradical generator) is, forexample, at least one kind of compound selected from the groupconsisting of 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one,2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one,2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl)phenyl]-1-butanone,2,4,6-trimethylbenzoyl diphenylphosphine oxide,bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium,and 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-O-benzoyloxime.

In a case of using electron rays as the active energy rays in theprocess of curing, addition of a photopolymerization initiator(photoradical generator) such as the above is not necessarily required.

The curing composition according to the present embodiment may furthercontain a thermoplastic resin, thermosetting resin, curing agent,leveling agent, antifoaming agent, dye, pigment, antioxidant,polymerization inhibitor, humectant, viscosity modifier, preservative,antibacterial agent, antiblocking agent, infrared absorber,electromagnetic shielding agent, antistatic agent, etc., as additives.The curing composition may contain a solvent.

The curing composition according to the present embodiment can be usedfor forming a cured film as a protective film that coats a surface ofvarious molded bodies.

Molded bodies of glass, ceramics, polycarbonate, polyester, urethane,acryl, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxyresin, polyolefin, various metals (stainless steel, etc.) can be citedas examples of the molded bodies that is protected by the cured film. Inparticular, when the curing composition according to the presentembodiment is used to coat a resin molded body surface that is poor inweather resistance in comparison to glass and ceramics, weatherresistance can be imparted and use can be made of lightness, softness,and other characteristics unique to resin molded bodies and are notpresent in glass substrates. The curing composition according to thepresent embodiment can be particularly preferably used for forming thecured film to protect the polycarbonate resin molded body.

The molded body protected by the cured film may have a flat shape likethat of a film, sheet, or plate or may have a three-dimensional shape oflarge height or thickness. In a case where the molded body has a flatshape, the cured film may be formed on one surface or both surfacesthereof. The cured film may coat a portion of a molded body surface ormay cover an entire surface.

FIG. 1 is a sectional view of an embodiment of a polycarbonate resinmolded body with cured film. The polycarbonate resin molded body 10 withcured film shown in FIG. 1 includes a plate-like polycarbonate resinmolded body 1 and a cured film 5 disposed on a surface of thepolycarbonate resin molded body 1. The cured film 5 has a film thicknessof normally approximately 1 to 50 μm. The cured film 5 is formed indirect contact with the surface of the polycarbonate resin molded body1. Although a primer layer may be disposed between the cured film 5 andthe molded body 1, the cured film 5 is excellent in adhesion to thepolycarbonate resin molded body 1 and thus a primary layer is notnecessarily required.

The polycarbonate resin molded body with cured film 5 may be obtained bya method that includes a step of forming a film of the active energyray-curing composition according to the present embodiment and a step offorming the cured film 5 by curing the formed film by irradiation ofactive energy rays. The film of the curing composition may be formed bycoating the curing composition. In a case where the curing compositioncontains a solvent, the solvent is removed by heating from the curingcomposition coated on the molding body 1 before irradiation of theactive energy rays.

EXAMPLES

The present invention shall now be described more specifically by way ofexamples. However, the present invention is not restricted to theexamples. In the following description, “parts” and “%” are based onmass unless noted in particular otherwise.

Details of abbreviations and product names indicated in the respectivemanufacturing examples and examples are as follows.

“LA87”: 3-(2,2,6,6-tetramethyl-4-piperidinyl)-2-methyl-1-propen-3-one(Adeka Stab LA Series, made by Adeka Corporation)

“FAMAC-4”: 2-(perfluorobutyl)ethyl methacrylate (made by Unimatec Co.,Ltd.)

“MMA”: methyl methacrylate

“4HBA”: 4-hydroxybutyl acrylate

“Karenz AOI”: (2-acryloyloxyethyl isocyanate, made by Showa Denko K. K.)

“RUVA93”: 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole(made by Otsuka Chemical Co., Ltd.)

“DPCA60”: (meth)acrylation product of an adduct of dipentaerythritol andε-caprolactone (compound with which n+m+l+o+p+q=6 in general formula(1))

“UA-1100H”: urethane oligomer (made by Shin-Nakamura Chemical Co., Ltd.,Mn=764, number of functional groups=6)

“X-22-2458”: reactive modified silicone oil (made by Shin-Etsu ChemicalCo., Ltd.)

“PGM-ST”: colloidal silica (made by Nissan Chemical Industries, Ltd.)

“Irgacure 184”: 1-hydroxycyclohexyl phenyl ketone (made by Ciba JapanLtd.)

“AIBN”: 2,2′-azobis(isobutyronitrile)

“EHQ”: hydroquinone monomethyl ether (made by Wako Pure ChemicalIndustries Co., Ltd.)

“DBTDL”: dibutyltin dilaurate (made by Wako Pure Chemical IndustriesCo., Ltd.)

Manufacturing Example 1

A reaction tank of a reaction container equipped with a stirrer, athermometer, a reflux condenser, a dripping apparatus, and a gasintroduction tube was charged with 250 parts of cyclohexanone andstirring at 80° C. was performed for 1 hour while blowing in nitrogengas. 100 parts of LA87 as the monomer (a1), 125 parts of 4HBA as themonomer (a2), 25 parts of MMA as the monomer (a3), 7.5 parts of AIBN,and 80.9 parts of cyclohexanone were charged into a dripping tank andthen dripped into the reaction tank over a period of 2 hours whilestirring the contents of the dripping tank. After the end of dripping,the dripping tank was washed with 34.7 parts of cyclohexanone and thewashing liquid was then placed in the reaction tank. After letting reactfor another 2 hours, a solution in which 2.5 parts of AIBN weredissolved in 22.5 parts of cyclohexanone was divided into three equalportions that were added on three occasions 30 minutes apart. 1 hourafter the third addition, the reaction liquid was cooled and taken outand a cyclohexanone solution of an acrylic-based prepolymer having ahydroxyl group was thereby obtained. The solids percentage was 39.56%.The hydroxyl value of the prepolymer was 185 (mgKOH/g).

The reaction tank was charged with 137.6 parts of the cyclohexanonesolution of the acrylic-based prepolymer, 0.05 parts of MEHQ as apolymerization inhibitor, 0.17 parts of DBTDL as a catalyst, and 39.6parts of cyclohexanone, and stirring at 60° C. was performed for 1 hourwhile blowing in dry air. Karenz AOI of an amount corresponding to 1mole of the isocyanate group with respect to 1 mole of the hydroxylgroup in the acrylic-based prepolymer was placed in the dripping tank asthe monomer (a4) and dripped into the reaction tank over a period of 1hour. When IR measurement of the reaction liquid was performed 3 hoursafter the end of dripping, a peak due to the isocyanate groupdisappeared and the reaction liquid was thus cooled and taken out. Asolution of the active energy ray-curing prepolymer A1 with a solidspercentage of 41.53% was thereby obtained.

The active energy ray-curing prepolymer A1 had a number averagemolecular weight Mn of 10000, a piperidinyl group equivalent of 842, anda (meth)acryloyl group equivalent of 430. The number average molecularweight Mn was determined as a polystyrene equivalent value using a GPC(gel permeation chromatography).

Manufacturing Example 2 and Manufacturing Example 3 ComparativeManufacturing Examples 1 and 2

Besides changing the types and amounts of the monomers (a1) to (a4) asshown in Table 1, solutions of active energy ray-curing prepolymers A2to A5 were obtained in the same manner as in Manufacturing Example 1.

TABLE 1 Comp. Comp. Manufacturing Manufacturing ManufacturingManufacturing Manufacturing Example 1 Example 2 Example 3 Example 1Example 2 Active energy A1 A2 A3 A4 A5 ray-curing prepolymer (A) AcrylicPiperidinyl LA87 — monomer group (a1) Acrylic Hydroxyl 4HBA monomergroup (a2) Acrylic Fluorine-atom- — FAMAC-4 — FAMAC-4 — monomercontaining (a3) functional group Other MMA — MMA — — functional groupAcrylic Isocyanate AOI monomer group (a4) Composition ratio of 40/50/1040/50/10 10/80/10 0/90/10 0/100/0 prepolymer (% by mass) a1/a2/a3Hydroxyl value of 185 185 299 336 374 prepolymer (mgKOH/g) Numberaverage 10000 11000 15000 16000 9000 molecular weight Mn Piperidinylgroup 842 842 4037 — — equivalent Fluorine-atom-containing — 4754 — 6013— functional group equivalent (Meth)acryloyl group 430 430 323 302 286equivalent

Example 1

The active energy ray-curing prepolymer A1 solution (containing the 10parts by weight of solids) obtained in Manufacturing Example 1, 10 partsby weight of RUVA93, 40 parts by weight of DPCA60, 40 parts by weight ofUA1100H, 7.5 parts by weight of PGM-ST, and 3 parts by weight ofIrgacure 184 were mixed to obtain an active energy ray-curingcomposition.

The active energy ray-curing composition was coated by a bar coater ontoa commercially available polycarbonate plate (made by Takiron Co.,Ltd.). The coating film was dried by heating at 120° C. for 3 minutesusing a hot air drying oven. Immediately thereafter, the coating filmwas cured by UV irradiation using a UV irradiation apparatus atconditions of a peak illuminance of 750 mW/cm² and an integrated lightquantity of 1000 mJ/cm² to obtain a cured film with a film thickness ofapproximately 10 μm. Wear resistance and weather resistance of the curedfilm were evaluated by methods described below. The evaluation resultsare shown in Table 2.

Examples 2 to 8 Comparative Examples 1 to 6

In likewise manner as in Example 1, active energy ray-curingcompositions and cured products were obtained in accordance withprescriptions shown in Tables 2 to 4 and were evaluated in the samemanner.

1) Wear Resistance

The wear resistance of each cured film was evaluated by a methodcomplying with ASTM D-1044. Specifically, a Taber wear tester (made byTaber Industries) was used to carry out a wear test of performing 500rotations at a load of 500 g using two abrasive wheels (CS-10F), and achange of haze (ΔH) before and after the test was measured using a hazemeter (made by Nippon Denshoku Industries Co., Ltd.). Wear resistancewas evaluated as being better the lower the ΔH.

2) Weather Resistance

5000 hours of an accelerated test was performed using a carbon arc typesunshine weather meter in compliance with JIS K5400. During the test,the state of each cured film was visually observed when suitable and thetimes at which cracking and spontaneous peeling were confirmed wererecorded respectively. The longer the time, the better the weatherresistance. The weather resistance of each cured film was judgedaccording to the following standards.

AA: Neither cracking nor spontaneous peeling occurred even after 5000hours.

A: The shorter of the times of occurrence of cracking and spontaneouspeeling was no less than 4000 hours and no more than 5000 hours.

B: The shorter of the times of occurrence of cracking and spontaneouspeeling was no less than 3000 hours and less than 4000 hours.

C: The shorter of the times of occurrence of cracking and spontaneouspeeling was less than 3000 hours.

Each cured film for which neither cracking nor spontaneous peelingoccurred even after 5000 hours was then observed visually and a film forwhich there was no surface soiling was judged as “A” and that for whichthere was surface soiling was judged as “C.”

TABLE 2 Example 1 2 3 4 Active A1 A2 A3 A4 energy Piperidinyl groupcontained ray-curing Fluorine-atom- — contained — — prepolymercontaining (A) functional group Active Benzotriazole RUVA93 energy groupray-curing compound (B) Active Compound (C1) DPCA60 energy having capro-ray-curing lactone-derived compound —(CH₂)⁵⁻ (C) Compound (C2) UA-1100Hhaving no capro- lactone-derived —(CH₂)⁵⁻ Reactive silicone — compoundInorganic SiO2 PGM-ST oxide particles (D) Photopolymerization initiatorIrgacure 184 Composition ratio (weight) 10/10/40/40 20/10/ 1/10/A/B/C1/C2 30/40 44/45 Wear % 8.7 8.3 9 8 resistance ΔH Weatherhour >5000 >5000 >5000 >5000 resistance (cracking) Weatherhour >5000 >5000 >5000 >5000 resistance (spontaneous peeling) JudgmentAA AA AA AA Weather resistance (surface A A A A soiling)

TABLE 3 Example 6 7 8 Active A1 A2 A3 energy Piperidinyl group containedray-curing Fluorine-atom- — contained — prepolymer containing (A)functional group Active Benzotriazole RUVA93 energy group ray-curingcompound (B) Active Compound (C1) DPCA60 energy having capro- ray-curinglactone-derived compound —(CH₂)⁵⁻ (C) Compound (C2) UA-1100H having nocapro- lactone-derived —(CH₂)⁵⁻ Reactive silicone x-22-2458 compoundInorganic SiO2 PGM-ST oxide particles (D) Photopolymerization initiatorIrgacure 184 Composition ratio (weight) 10/10/40/40 20/10/ A/B/C1/C230/40 Wear % 4.5 5.1 6.5 resistance ΔH Weather hour >5000 >5000 >5000resistance (cracking) Weather hour >5000 >5000 >5000 resistance(spontaneous peeling) Judgment AA AA AA Weather resistance (surface A AA soiling)

TABLE 4 Comparative Example 1 2 3 4 5 6 Active A1 A4 A5 LA87 — A1 energyPiperidinyl group contained — — — contained ray-curingFluorine-atom-containing — F — — — prepolymer functional (A) groupActive Benzotriazole group — RUVA RUVA RUVA — RUVA energy 93 93 93 93ray-curing compound (B) Active Compound (C1) DPCA60 energy havingray-curing caprolactone-derived compound —(CH₂)₅— (C) Compound (C2) notUA-1100H having caprolactone-derived —(CH₂)₅— Reactive silicone —compound Inorganic SiO2 PGM-ST — oxide particles (D) Photopolymerizationinitiator Irgacure 184 Composition ratio (weight) 10/0/45/45 10/10/40/4010/10/40/40 4/10/43/43 0/0/50/50 10/10/40/40 A/B/C1/C2 Wear % 4.5 4.5 44.8 3 12.2 resistance ΔH Weather hour 1500 3000 2500 >5000 1500 >5000resistance (cracking) Weather hour 2500 3000 3000 >5000 1500 >5000resistance (spontaneous peeling) Judgment C B C AA C AA Weatherresistance (surface — — — C — A soiling)

From the results shown in Tables 2 to 4, it was confirmed that a curedfilm having adequately excellent weather resistance and wear resistancecan be formed by the present invention.

INDUSTRIAL APPLICABILITY

By coating the active energy ray-curing composition according to thepresent invention on various parts to form a cured film, the parts canbe protected from ultraviolet, etc. The active energy ray-curingcomposition according to the present invention can be used to form acured film to protect a surface of a part that is used under anenvironment in which it is exposed to light like sunlight, etc., or hitby sand and dust, etc. indoors or outdoors. The cured film can beutilized for uses of a building material, a display of a mobile phone,portable game device, portable music player and digital camera, etc., asolar battery panel, a window glass, wood, and papers, etc.

REFERENCE SIGNS LIST

1 . . . polycarbonate resin molded body, 5 . . . cured film, 10 . . .polycarbonate resin molded body with cured film.

1. An active energy ray-curing composition comprising: an active energyray-curing prepolymer (A) obtainable by a reaction of an acrylic-basedprepolymer having a hydroxyl group and an acrylic monomer (a4) having anisocyanate group and a (meth)acryloyl group; an active energy ray-curingcompound (B) having a benzotriazole group and a (meth)acryloyl group;another active energy ray-curing compound (C) having a (meth)acryloylgroup and being different from the (A) component and the (B) component;and inorganic oxide particles (D), the acrylic-based prepolymer havingthe hydroxyl group being a copolymer including as monomer units: anacrylic monomer (a1) having a piperidinyl group and a (meth)acryloylgroup; an acrylic monomer (a2) having a hydroxyl group and a(meth)acryloyl group; and another monomer (a3).
 2. The active energyray-curing composition according to claim 1, wherein the active energyray-curing prepolymer (A) has a number average molecular weight of 3000to
 100000. 3. The active energy ray-curing composition according toclaim 1, wherein the active energy ray-curing prepolymer (A) has a(meth)acryloyl group equivalent of 250 to
 1600. 4. The active energyray-curing composition according to claim 1, wherein the monomer (a3)comprises a compound having a functional group that contains a fluorineatom.
 5. The active energy ray-curing composition according to claim 4,wherein the functional group that contains a fluorine atom is aperfluoroalkyl group.
 6. The active energy ray-curing compositionaccording to claim 1, wherein the active energy ray-curing compound (C)comprises a compound (C1) having a (meth)acryloyl group and a groupexpressed by —(CH₂)₅—.
 7. The active energy ray-curing compositionaccording to claim 6, wherein the compound (C1) having the(meth)acryloyl group and the group expressed by —(CH₂)₅— is a compoundexpressed by the following general formula (1).

[In formula (1), R¹ indicates a hydrogen atom or a methyl group, aplurality of R¹ in the same molecule may be the same or different, andn, m, l, o, p, and q indicate integers satisfying n+m+l+o+p+q=1 to 12.]8. The active energy ray-curing composition according to claim 7,wherein n, m, l, o, p, and q are integers satisfying n+m+l+o+p+q=6 to12.
 9. The active energy ray-curing composition according to claim 6,wherein the active energy ray-curing compound (C) further comprises acompound (C2) having a (meth)acryloyl group and no group expressed by—(CH₂)₅—.
 10. The active energy ray-curing composition according toclaim 9, wherein the compound (C2) having the (meth)acryloyl group andno group expressed by —(CH₂)₅— is a urethane compound having an averageof 2 to 15 (meth)acryloyl groups and a urethane group.
 11. The activeenergy ray-curing composition according to claim 9, wherein the compound(C2) having the (meth)acryloyl group and no group expressed by —(CH₂)₅—has a number average molecular weight of 500 to
 10000. 12. The activeenergy ray-curing composition according to claim 9, wherein the activeenergy ray-curing compound (C) further comprises a silicone oil (C3)having a (meth)acryloyl group.
 13. The active energy ray-curingcomposition according to claim 1, wherein the inorganic oxide particles(D) are SiO₂ particles.
 14. The active energy ray-curing compositionaccording to claim 1, wherein on the basis of the total amount of the(A) component, the (B) component, and the (C) component, a proportion ofthe (A) component is 1 to 50% by mass, a proportion of the (B) componentis 1 to 20% by mass, and a proportion of the (C) component is 30 to 95%by mass.
 15. The active energy ray-curing composition according to claim12, wherein on the basis of the total amount of the (A) component, the(B) component, and the (C) component, a proportion of the (A) componentis 1 to 50% by mass, a proportion of the (B) component is 1 to 20% bymass, a proportion of the (C1) component is 5 to 60% by mass, aproportion of the (C2) component is 20 to 80% by mass, and a proportionof the (C3) component is 0.01 to 2% by mass.
 16. The active energyray-curing composition according to claim 1, wherein with respect to 100parts by weight of the total amount of the (A) component, the (B)component, and the (C) component, an amount of the inorganic oxideparticles (D) is 0.1 to 20 parts by weight.
 17. A polycarbonate resinmolded body with cured film comprising: a polycarbonate resin moldedbody; and a cured film disposed on a surface of the polycarbonate resinmolded body and formed by curing of the active energy ray-curingcomposition according to claim
 1. 18. A method for manufacturing apolycarbonate resin molded body with cured film, the method comprising:a step of forming a film of the active energy ray-curing compositionaccording to claim 1 on a surface of a polycarbonate resin molded body;and a step of curing the formed film by irradiation of active energyrays to form a cured film.